JP2011046906A - Curable resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin composition exhibiting practically sufficient curability and not containing a tributyl tin compound having anxiety about toxicity. <P>SOLUTION: The curable resin composition containing two kinds curable resins containing in a molecule a crosslinkable silyl group-containing functional group having a specific chemical structure, an octyl tin compound and an aminosilane compound of a specific chemical structure having in a molecule an amino group and a crosslinkable silyl group and not containing the tributyl tin compound is used. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a curable resin composition containing a crosslinkable silyl group, which can be cured at room temperature, and more specifically, is capable of reducing environmental burden and has a necessary and sufficient curing rate. The present invention relates to a resin composition.

  Curable resins having a crosslinkable silyl group in the molecule are widely used as base polymers for sealants, adhesives, pressure-sensitive adhesives, paints and the like. This curable resin is also called a moisture curable polymer because it cures when the crosslinkable silyl group is hydrolyzed and crosslinked with moisture in the atmosphere. In particular, curable resins in which the crosslinkable silyl group is an alkoxysilyl group are widely used because of their safety and low odor (Patent Document 1 and Patent Document 2).

  Among curable resins, dialkoxysilyl group-terminated polymers are generally used with a good balance of performance. Conventionally, dibutyltin compounds have been widely used to cure these dialkoxysilyl group-terminated polymers at a practical curing speed. However, the dibutyltin compounds have recently been feared for their toxicity. There is a potential problem that the tributyltin compound may be mixed in a trace amount.

  As a method for improving the curing speed, a combination system of a curable resin whose terminal structure is a dialkoxysilyl group and a trialkoxysilyl group (Patent Document 3), an α-position carbon bonded to a silicon atom contained in a crosslinkable silyl group A curable resin having a group to which heteroatoms such as oxygen, nitrogen, and sulfur having an unshared electron pair are bonded has been proposed (Patent Document 4). However, even in a mixed system as shown in Patent Document 3, a dibutyltin compound is frequently used as a curing catalyst. In a special curable resin as shown in Patent Document 4, an organometallic catalyst such as an organic tin compound is used. Essentially, amine catalyst systems are used that are essentially free of.

JP-A-52-73998 Japanese Unexamined Patent Publication No. Sho 63-112642 Japanese Patent No. 3341453 JP 2005-514504 Gazette

  On the other hand, there is an octyltin compound as an organotin catalyst that has no risk of mixing with a tributyltin compound because of its manufacturing process. However, since the octyltin compound is less active than the butyltin compound, there is a problem in obtaining a practically sufficient curability with the specifications of the single substance.

  The problem to be solved by the present invention is to obtain a curable resin composition that exhibits practically sufficient curability and does not contain a tributyltin compound that is concerned about toxicity.

  In order to solve such problems, the present inventors, as a result of intensive studies, in a blended system in which an aminosilane compound is mixed with a specific combination of curable resin mixture, the octyltin compound has a lower activity than the butyltin compound. It has been found that a curable resin composition exhibiting the same curability as that of a butyltin compound can be obtained even when using, and the present invention has been completed. The present invention includes the following first to sixth inventions.

That is, the first invention is a curable resin (P1) containing a crosslinkable silyl group-containing functional group represented by the following formula (1) in the molecule;
A curable resin (P2) containing a crosslinkable silyl group-containing functional group represented by the following formula (2) in the molecule;
An octyltin compound (B);
An aminosilane compound (C) having an amino group and a crosslinkable silyl group in the molecule as represented by the compound represented by the following formula (3);
And a curable resin composition characterized by not containing a tributyltin compound. By using together the two types of curable resins having a crosslinkable silyl group-containing functional group, a curable resin composition exhibiting the same curability as a butyltin compound can be obtained even when an octyltin compound is used.

_{^{-X-SiR 1 (OR 2)}} 2 ··· formula (1)
(However, X is a hydrocarbon group having 2 or more carbon atoms, R ¹ is a hydrocarbon group having 1 to 10 carbon atoms, R ² is a phenyl group, an alkyl group having 1 to 6 carbon atoms, and 2- ( Butoxy) one or more groups selected from organic groups having 1 to 10 carbon atoms represented by ethyl group

^{_{-W-CH 2 -SiR 3 a (}} OR 4) 3-a ··· formula (2)
(W is a bonding functional group in which a hetero atom having a lone pair is bonded to a methylene group bonded to a silicon atom contained in a crosslinkable silyl group, and R ³ is a hydrocarbon having 1 to 10 carbon atoms. R ⁴ is a group of at least one selected from a phenyl group, an alkyl group having 1 to 6 carbon atoms, and an organic group having 1 to 10 carbon atoms typified by 2- (butoxy) ethyl group, 0, 1 or 2 are shown respectively)

R ⁵ R ⁶ N—R ⁷ —SiR ⁸ _b (OR ⁹ ) _3-b Formula (3)
(However, R ⁵ and R ⁶ are organic groups or hydrogen atoms, R ⁷ is an organic group in which a hetero atom is not bonded to a carbon atom bonded to a silicon atom contained in a crosslinkable silyl group, and R ⁸ is a carbon number. 1 to 10 hydrocarbon groups, R ⁹ is a kind selected from a phenyl group, an alkyl group having 1 to 6 carbon atoms, and an organic group having 1 to 10 carbon atoms typified by 2- (butoxy) ethyl group The above groups, b represents 0, 1 or 2, respectively)

  The second invention relates to the curable resin composition according to the first invention, wherein the curable resin (P1) further contains a urethane bond and / or a urea bond in the molecule. In the present invention, the active hydrogen in the urethane bond and / or urea bond of the curable resins (P1) and (P2) in the molecule may be substituted with an organic group. Therefore, in the present invention, allophanate bonds also belong to the category of urethane bonds, and burette bonds also belong to the category of urea bonds. By using a curable resin having a urethane bond and / or a urea bond in the molecule, a curable resin composition exhibiting a curability equivalent to that of a butyltin compound can be obtained more easily even if an octyltin compound is used.

  The third invention relates to the curable resin composition according to the first or second invention, wherein a = 1 in the above formula (2). Such a curable resin is preferable because of its relatively excellent storage stability.

4th invention is related with the sealant composition which has the curable resin composition which concerns on any one of 1st-3rd invention as a main component of a sclerosing | hardenable component.
5th invention is related with the adhesive composition which has the curable resin composition which concerns on any one of 1st-3rd invention as a main component of a sclerosing | hardenable component.
6th invention is related with the adhesive precursor composition which has the curable resin composition which concerns on any one of 1st-3rd invention as a main component of a sclerosing | hardenable component.
By using the curable resin composition according to the present invention as the main component of the curable component, it has a practically sufficient curing rate and also contains no sealant composition, adhesive composition, and pressure sensitive adhesive precursor composition that does not contain a tributyltin compound. Can be prepared.

  The curable resin composition according to the present invention has an effect of providing a necessary and sufficient curing rate while ensuring a reduction in environmental burden and safety.

  Hereinafter, the best mode for carrying out the present invention will be described in detail. In addition, this invention is not limited only to these illustrations, Of course, a various change can be added in the range which does not deviate from the summary of this invention.

[Curable resin (P1)]
The curable resin (P1) in the present invention is a curable resin having a crosslinkable silyl group-containing functional group represented by the above formula (1) in the molecule. The curable resin (P1) used in the present invention is preferably liquid at room temperature in terms of workability and the like. In the crosslinkable silyl group-containing functional group, a hydrocarbon group (X) having 2 or more carbon atoms is bonded to a silicon atom, and this is bonded to the main chain skeleton. The silicon atom constituting the crosslinkable silyl group is bonded with two alkoxyl groups (OR ² ) as a crosslinkable group in addition to the bond with the hydrocarbon group X, and with a hydrocarbon group (R ¹ ) is connected. The alkoxyl group (OR ² ) is preferably a methoxy group, an ethoxy group, a propoxy group or a butoxy group, more preferably a methoxy group or an ethoxy group. The hydrocarbon group (R ¹ ) bonded to the remaining bond of the silicon atom is preferably a methyl group, an ethyl group, a propyl group or a butyl group, more preferably a methyl group or an ethyl group. .

  The molecular weight of the curable resin (P1) is not particularly limited, but is preferably 1,000 to 60,000, more preferably 2,000 to 40,000, and particularly preferably 3,000 to 20,000. If the molecular weight is less than 1,000, the crosslink density becomes too high and may become brittle. If the molecular weight exceeds 60,000, the viscosity becomes high and workability may be deteriorated, and the use conditions may be limited.

  As the main chain skeleton of the curable resin (P1), polyoxyalkylene, vinyl polymer (eg, polyacrylate, polymethacrylate, etc.), saturated hydrocarbon polymer, unsaturated hydrocarbon polymer, polyester, polycarbonate, polydimethyl One or more skeletons selected from main chain skeletons generally used for silicone resins such as siloxane and modified silicone resins are employed. In particular, it is preferably polyoxyalkylene and / or poly (meth) acrylate from the viewpoints of easy availability and film properties of the cured product. Here, “essentially” means that the structure is a main element of a repeating unit which is the main chain skeleton of the curable resin (P1). Moreover, this structure may be contained independently in curable resin (P1), and 2 or more types may be contained.

  A large number of commercially available curable resins (P1) are sold as silicone resins or modified silicone resins. For example, Kaneka's Silyl series, Kaneka MS polymer series, MA series, EP series, SA series, OR series, Exastar series made by Asahi Glass, Silane modified polyalphaolefin made by Degussa Japan, Shin-Etsu Chemical Co., Ltd. Examples thereof include, but are not limited to, KC series, KR series, X-40 series, XPR series manufactured by Toagosei Co., Ltd., Actflow series manufactured by Soken Chemical Co., Ltd., and the like.

  The curable resin (P1) in the present invention is preferably a curable resin having a urethane bond and / or a urea bond in the molecule in addition to the crosslinkable silyl group. In the present invention, the active hydrogen in the urethane bond and / or urea bond that the curable resin (P1) has in the molecule may be substituted with an organic group. Therefore, in the present invention, allophanate bonds also belong to the category of urethane bonds, and burette bonds also belong to the category of urea bonds.

  Such a curable resin may be synthesized by a conventionally known method. For example, a method of reacting an isocyanate group-terminated polymer with an amino group-containing alkoxysilane compound (or a mercapto group-containing alkoxysilane compound), a method of reacting a hydroxyl group-terminated polyol with an isocyanate group-containing alkoxysilane compound, and the like are known. More specifically, it can be easily synthesized by the methods described in Japanese Patent No. 3030020, Japanese Patent No. 3343604, Japanese Patent Application Laid-Open No. 2005-54174, and the like.

[Curable resin (P2)]
The curable resin (P2) in the present invention is a curable resin having a crosslinkable silyl group-containing functional group represented by the above formula (2) in the molecule. In the present invention, as represented by the above formula (2), hetero atoms such as oxygen, nitrogen and sulfur having an unshared electron pair are bonded to the α-position carbon bonded to the silicon atom contained in the crosslinkable silyl group. This chemical structure is expressed as “α-silane structure”. It is known that by selecting an α-silane structure, the moisture reactivity is extremely higher than that of a normal crosslinkable silyl group.

  A bonding functional group (W) in which a hetero atom having an unshared electron pair is bonded to a silicon atom constituting the crosslinkable silyl group via a methylene group is bonded to the crosslinkable silyl group-containing functional group. . The bond functional group (W) is a structure that connects the crosslinkable silyl group and the main chain, and if a heteroatom having an unshared electron pair is bonded to a methylene group bonded to a silicon atom constituting the crosslinkable silyl group. Specific examples include (thio) urethane bond, (thio) urea bond, (thio) substituted urea bond, (thio) ester bond, (thio) ether bond, and the like. Further, the crosslinkable silyl group is bonded to the main chain skeleton via the bonding functional group (W).

In addition to the bond with the methylene group, the silicon atom has 1 to 3 alkoxy groups (OR ⁴ ) as hydrolyzable groups and 2 hydrocarbon groups (R ³ ) as the remaining bonds. There are ~ 0 bonds.
Here, the alkoxyl group (OR ⁴ ) is preferably a methoxy group, an ethoxy group, a propoxy group, or a butoxy group, and more preferably a methoxy group or an ethoxy group. The hydrocarbon group (R ³ ) bonded to the remaining bond of the silicon atom is preferably a methyl group, an ethyl group, a propyl group, a butyl group, or a phenyl group, and is preferably a methyl group, an ethyl group, or a propyl group. A butyl group is more preferable, and a methyl group and an ethyl group are particularly preferable.

  The crosslinkable silyl group of the curable resin (P2) is an alkyldialkoxysilyl group (a = 1 in the formula (2)) or a trialkoxysilyl group (a = 0 in the formula (2)). However, it is preferable from the viewpoint of availability, modulus of cured product, and the like, and an alkyldialkoxysilyl group (in formula (2), a = 1) is particularly preferable because it is easy to balance the physical properties of the cured product and the curing rate. preferable.

  The molecular weight of the curable resin (P2) is not particularly limited, but is preferably 1,000 to 80,000, more preferably 1,500 to 60,000, and particularly preferably 2,000 to 40,000. If the molecular weight is less than 1,000, the cured product obtained may have brittle physical properties because the crosslinking density becomes too high. If the molecular weight exceeds 80,000, the viscosity increases and the workability deteriorates. In some cases, blending may be limited, such as requiring a large amount of plasticizer.

  As the main chain skeleton of the curable resin (P2), polyoxyalkylene, vinyl polymer (eg, polyacrylate, polymethacrylate, etc.), saturated hydrocarbon polymer, unsaturated hydrocarbon polymer, polyester, polycarbonate, polydimethyl One or more skeletons selected from main chain skeletons generally used for silicone resins such as siloxane and modified silicone resins are employed. In particular, it is preferably polyoxyalkylene and / or poly (meth) acrylate from the viewpoints of easy availability and film properties of the cured product. Here, “essentially” means that the structure is a main element of a repeating unit which is a main chain skeleton of the curable resin (P2). Moreover, this structure may be contained independently in curable resin (P2), and 2 or more types may be contained.

  In order to obtain the curable resin (P2), synthesis may be performed by a conventionally known method. For example, a method of reacting an isocyanate methylalkoxysilane compound with a polyol compound, a polyol compound and a polyisocyanate compound are reacted to synthesize a urethane prepolymer, and then an alkoxysilyl such as a mercaptomethylalkoxysilane compound or an aminomethylalkoxysilane compound is synthesized with the urethane prepolymer. A method of reacting a compound in which a hetero atom having an active hydrogen group is bonded to the α-position carbon of the silicon atom of the group is known. Here, trialkoxysilane, alkyldialkoxysilane, and dialkylalkoxysilane are collectively referred to as “alkoxysilane”. The amino group of the aminomethylalkoxysilane compound may be a primary amino group or a secondary amino group, but the viscosity of the curable resin (P2) is higher when it is a secondary amino group. It is preferable because it can be adjusted to a relatively low viscosity. The aminomethylalkoxysilane compound having a secondary amino group can be derived from an aminomethylalkoxysilane compound having a primary amino group. Specifically, a method of reacting an aminomethylalkoxysilane compound having a primary amino group with a compound having a functional group causing a conjugate addition reaction with an amino group such as an α, β-unsaturated carbonyl compound or an acrylonitrile compound. Etc. are raised. Furthermore, it can be easily synthesized by the methods described in JP-T-2004-518801, JP-T-2004-536957, JP-T-2005-501146, and the like.

  Examples of commercially available curable resin (P2) include GENIOSIL STP-E10, GENIOSIL STP-E30 manufactured by Wacker Chemie AG.

  In the present invention, the curable resins (P1) and (P2) having the above two types of crosslinkable silyl group-containing functional groups are used in combination, so that the curable resin exhibits the same curability as a butyltin compound even when an octyltin compound is used. This is based on the knowledge that a resin composition can be obtained.

[About Octyltin Compound (B)]
In the octyltin compound (B) in the present invention, among the organic tin compounds, the organic group portion is a hydrocarbon group having 8 carbon atoms (including not only an octyl group but also an isomer such as a 2-ethylhexyl group). A monoalkyltin compound or a dialkyltin compound, which refers to a compound or substance that acts as a curing accelerator for a crosslinkable silyl group.

  Specific examples of octyltin compounds include dioctyltin distearate, dioctyltin oxide, dioctyltin dilaurate, dioctyltin diacetate, dioctyltin dineodecate, dioctyltin bisethylmalate, dioctyltin bisoctylmalate, dioctyltin bisisooctylthioglycol Examples thereof include, but are not limited to, rate, octyltin malate, dioctyltin dimethoxide, a reaction product of dioctyltin oxide and phthalic acid diester, a reaction product of dioctyltin oxide and ethyl silicate, and the like. Moreover, the octyl tin compound is marketed and can use those commercial products in this invention. Commercially available octyltin compounds include Neostan U-800, Neostan U-810, Neostan U-820, Neostan U-830, Neostan U-840, Neostan U-850, Neostan U-860, Neostan U-870, Neostan U-870 -780, Neostan S-1 (the product name manufactured by Nitto Kasei Co., Ltd.) and the like can also be used.

[Aminosilane compound (C)]
The aminosilane compound (C) in the present invention is a compound having an amino group and a crosslinkable silyl group in the molecule. As the aminosilane compound (C), since the low molecular aminosilane compound having an α-silane structure is highly toxic, the aminosilane compound not having the α-silane structure, that is, the nitrogen atom of the amino group and the silicon atom of the crosslinkable silyl group An aminosilane compound in which two or more carbon atoms are bonded to each other is preferable.

  Examples of the aminosilane compound (C) include the aminosilane compound (C) represented by the above formula (3), the condensation reaction product of the aminosilane compound (C) alone, or the aminosilane compound (C) and the following formula (4). Examples thereof include condensation reaction products with other silane compounds as exemplified by the silane compound (C1). Among these, the aminosilane compound (C) or the condensation reaction product of the aminosilane compound (C) alone is more preferable because the effect of the amino group in the aminosilane compound (C) can be expressed more easily.

Si (R ¹⁰ ) (R ¹¹ ) (R ¹² ) (OR ¹³ ) (4)
(In the formula, R ¹⁰ , R ¹¹ , and R ¹² are a phenyl group, an alkyl group having a molecular weight of 500 or less, a mercaptopropyl group, a ureidopropyl group, a phenoxy group, and an alkoxy group having 1 to 6 carbon atoms, 2- Each represents one or more groups selected from organic groups having a molecular weight of 500 or less typified by (butoxy) ethoxy groups, R ¹³ represents a phenyl group, an alkyl group having 1 to 6 carbon atoms, and a 2- (butoxy) ethyl group. And one or more groups selected from organic groups having 1 to 12 carbon atoms represented by

  The amino group contained in the aminosilane compound (C) may be any of primary, secondary, and tertiary amino groups, but the curable resin composition according to the present invention may be an adhesive, a sealing material, In the case where it is used for an application requiring adhesiveness such as an adhesive, a primary or secondary amino group that exhibits the effect of imparting adhesiveness is more preferable, and a primary amino group is particularly preferable. Moreover, the amino group contained in the said aminosilane compound (C) may be one, and may be two or more. The crosslinkable silyl group contained in the aminosilane compound (C) is an alkyl dialkoxysilyl group (b = 1) or a trialkoxysilyl group (b = 0) as exemplified by the aminosilane compound (C). Is preferable because it is easily available and the modulus of the cured product can be easily adjusted. The number of crosslinkable silyl groups contained in the aminosilane compound (C) may be one or two or more.

  Specific examples of the aminosilane compound (C) include 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2- Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2 -Aminoethyl) -3-aminopropylmethyldiethoxysilane, 4-amino-3-dimethylbutyltrimethoxysilane, 4-amino-3-dimethylbutylmethyldimethoxysilane, 4-amino-3-dimethylbutyltriethoxysilane, 4-Amino-3-dimethylbutylmethyl diet Sisilane, bis (3-trimethoxypropyl) amine, bis (3-methyldimethoxypropyl) amine, N-phenylaminopropyltrimethoxysilane, N-phenylaminopropylmethyldimethoxysilane, N-ethylaminoisobutyltrimethoxysilane, N Aminosilane compounds such as ethylaminoisobutylmethyldimethoxysilane, N-butylaminopropyltrimethoxysilane, N-butylaminopropylmethyldimethoxysilane, diethylenetriaminopropyltrimethoxysilane, and N- (2-propenyl) aminopropyltrimethoxysilane; For example, but not limited to. Further, a ketimine silane compound such as 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine is also substantially included in the aminosilane compound (C) because a primary amino group is generated by moisture. include. Among them, the use of 3-aminopropyltrimethoxysilane or N- (2-aminoethyl) -3-aminopropyltrimethoxysilane is easy to obtain and has a high curing acceleration effect. It is preferable from the point. Further, it is known that a cured product in which an aminosilane compound is blended is generally easily yellowed by heat or light. When used in applications where yellowing is not preferred, 4-amino-3-dimethylbutyltrimethoxysilane, 4-amino-3-dimethylbutylmethyldimethoxysilane, 4-amino-3-dimethylbutyltriethoxysilane Aminosilanes with a small number of hydrogen atoms bonded to the β-position carbon of nitrogen atoms, such as 4-amino-3-dimethylbutylmethyldiethoxysilane, N-ethylaminoisobutyltrimethoxysilane, N-ethylaminoisobutylmethyldimethoxysilane, etc. Use of a compound is preferable because yellowing is reduced.

[Silane Compound (C1)]
Specific examples of the silane compound (C1) include methyltrimethoxysilane, dimethyldimethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, tetraethoxysilane, Examples include dimethoxydiethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-ureidopropyltrimethoxysilane. Of these, methyltrimethoxysilane and dimethyldimethoxysilane are preferably used from the viewpoint of easy condensation reaction with the aminosilane compound (C).

  The aminosilane compound (C) alone or the condensation reaction product of the aminosilane compound (C) and the silane compound (C1) may be synthesized by a conventionally known method. Specifically, a method of reacting the aminosilane compound (C) with water or a method of reacting the aminosilane compound (C) and the silane compound (C1) with water can be mentioned. The aminosilane compound (C) alone or the condensation reaction product of the aminosilane compound (C) and the silane compound (C1) is commercially available, and they can be used in the present invention. Examples of commercially available products include MS3301 (trade name, manufactured by Chisso Corporation), MS3302 (trade name, manufactured by Chisso Corporation), X-40-2651 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.

  The aminosilane compound (C) may be appropriately selected in order to obtain desired cured film properties and / or curing speed, and may be used alone or in combination of two or more. Among the aminosilane compounds (C), 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) ) -3-Aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, 4-amino-3-dimethylbutyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyl Triethoxysilane, N-ethylaminoisobutyltrimethoxysilane and condensation reaction products derived therefrom are preferable because they are easily available, and 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl)- 3-aminopropyltrimethoxysilane N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 4-amino-3-dimethylbutyltrimethoxysilane, and N- (2-aminoethyl) -3-aminopropyltrimethoxysilane are effective for curing. From the viewpoint of high, 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane are more preferable. In the case where the curable resin composition according to the present invention is used for applications requiring adhesiveness such as an adhesive, a sealing material, and a pressure-sensitive adhesive, it is particularly preferable since the effect of imparting adhesiveness is high.

[About the amount]
In this invention, 2-1000 mass parts of curable resin (P2) is preferable with respect to 100 mass parts of curable resin (P1), 4-800 mass parts is more preferable, 6-500 mass parts is especially preferable, 10-200 mass parts is the most preferable. If the amount is less than 2 parts by mass, the effect of curing speed may not be sufficiently exhibited. If the amount is more than 1000 parts by mass, the ratio of the curable resin (P1) is relatively small, so that the storage stability may be deteriorated.

  The addition amount of the aminosilane compound (C) is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the total of the curable resins (P1) and (P2). 1.0 to 10 parts by mass is particularly preferable. If the amount is less than 0.1 parts by mass, the effect of imparting adhesiveness may not be sufficiently exhibited. If the amount exceeds 30 parts by mass, the dilution effect becomes too large and the functions of the curable resins (P1) and (P2) are sufficiently exhibited. May not be. The aminosilane compound (C) may be appropriately selected in order to obtain desired cured film properties and / or curing speed, and may be used alone or in combination of two or more.

[Other ingredients]
In the curable resin composition according to the present invention, any conventionally known compound or substance can be blended as other components. For example, various curable resins (epoxy resins, urethane resins, oxetane resins, cyclic carbonate resins) other than the curable resins (P1) and (P2) used in the present invention and non-curable resins (acrylic resins) , Polycarbonate resin, etc.), non-tin based metal catalyst, acidic catalyst, silane coupling agent such as γ-glycidoxypropyltrimethoxysilane, filler such as calcium carbonate, clay, hydrophilic or hydrophobic silica based powder , Phenolic resin, terpene resin, tackifier such as terpene phenol resin, thixotropic agent such as amide wax, dehydrating agent such as calcium oxide, diluent, plasticizer, flame retardant, various liquid oligomers, anti-aging agent, UV absorption Agent, pigment, titanate coupling agent, aluminum coupling agent, drying oil, various solvents, etc. can be blended.

  As the non-tin-based metal catalyst, as a compound mainly composed of a group 1 alkali metal metal element, lithium naphthenate, sodium stearate, potassium octylate and the like are group 2 alkaline earth metal metals. As the compound mainly composed of elements, magnesium naphthenate, calcium octylate, barium octylate, etc., and as compounds composed mainly of transition metal-based metal elements, yttrium octylate, titanium tetrabutoxide, titanium acetylacetone complex, titanium diisopropoxy, etc. Bis (ethyl acetoacetate), zirconium tetrapropoxide, zirconium tributoxy monoacetylacetonate, zirconium monobutoxyacetylacetonate bis (ethylacetoacetate), vanadyl acetylacetonate, vanadium acetyl Acetonate, chromium acetylacetone complex, manganese acetylacetone complex, iron octylate, cobalt naphthenate, cobalt octylate, nickel acetylacetone complex, copper naphthenate, copper acetylacetone complex, etc., mainly composed of group 12 zinc group metal elements Zinc acetylacetonate monohydrate, zinc naphthenate, zinc octylate, etc. are compounds mainly composed of Group 13 earth metal elements, such as aluminum acetylacetone complex, aluminum tributoxide, aluminum ethylacetoacetate complex Indium acetylacetone complex and the like are mainly composed of a group 15 nitrogen group metal element, such as bismuth naphthenate and bismuth tris (2-ethylhexanoate). Specific examples of commercially available products include nursem aluminum, nursem chromium, nursem first cobalt, nursem second cobalt, nursem copper, nursem ferric iron, nursem nickel, nursem vanadyl, nursem zinc, nursem indium, and nursem magnesium. , Nursem manganese, nursem yttrium, nursem cerium, nursem strontium, nursem palladium, nursem barium, nursem molybdenyl, nursem lanthanum, nursem zirconium, nursem titanium, naphthex Co series, Nikka Octix Co series, Naphthex Mn series, Nikka octix Mn series, naphthex Zn series, Nikka octix Zn series, naphthex Ca series, Nikka octix Ca series, naphth K series, Nikka octix K series, Nikka octix Bi series, Bidecanoic acid Bi series, Pecat series, PA series, naphthex Zr series, Nikka octix Zr series, naphthex Fe series, Nikka octix Fe series, naphthex Mg Series, Naftex Li series, Naphtex Cu series, Naphtex Ba series, Nikka Octix Reals series, Nikka Octix Ni series, etc. (above, Nippon Kagaku Sangyo Co., Ltd. trade name), Olga Chicks ZA-40, Olga Chicks ZA-65 , ORGATICS ZC-150, ORGATICS ZC-540, ORGATICS ZC-570, ORGATICS ZC-580, ORGATICS ZC-700, ORGATI KUZZ-320, ORGATICS TA-10, ORGATICS TA-25, ORGATICS TA-22, ORGATICS TA-30, ORGATICS TC-100, ORGATICS TC-401, ORGATICS TC-200, ORGATICS TC -750, Olgatics TPHS, etc. (above, trade names manufactured by Matsumoto Fine Chemical Co., Ltd.), SNAPCURE 3020, SNAPCURE 3030, VERTEC NPZ, etc. (above, trade names manufactured by Johnson Matthey), Neostan U-600, Neostan U-660 etc. Nitto Kasei Co., Ltd. product name), Kenriact NZ01, Kenriact NZ33, Kenriact NZ39, etc. (above, product name produced by Kenrich), Aluminum Etoxide, AIPD, PADM, AMD, ASBD, ALCH, LCH-TR, aluminum chelate M, aluminum chelate D, aluminum chelate A, algomer, algomer 800AF, algomer 1000SF, pre-act ALM, etc. (above, product names manufactured by Kawaken Fine Chemical Co., Ltd.), A-1, B-1, TOT, TOG , T-50, T-60, A-10, B-2, B-4, B-7, B-10, TBSTA, DPSTA-25, S-151, S-152, S-181, etc. Nippon Soda Co., Ltd. trade name), Octope series, Kerop series, Olipe series, Acetop series, Chemihope series (trade name made by Hope Pharmaceutical Co., Ltd.) and the like. Among these, when it is at least one selected from the group consisting of zirconium compounds, titanium compounds, aluminum compounds, and bismuth compounds, it is possible to reduce the environmental burden, to ensure safety, and to achieve a curing rate that can withstand actual use. Is preferable in that it is easily obtained.

  The curable resin composition according to the present invention can be used as a one-part liquid or a two-part or more multi-part liquid, but in any case, the crosslinkable silyl groups shrink in the presence of moisture. It is cured by polymerization. Therefore, when used as a one-component composition, it is handled in an airtightly sealed state so as not to come into contact with air (water in the air) during storage or transportation. And if it opens and uses it in arbitrary places at the time of use, it will contact with the water | moisture content in air and a curable resin will harden | cure.

  The curable resin composition according to the present invention can be used for all applications to which a conventional curable resin has been applied. For example, it can be used as an adhesive, sealant, pressure-sensitive adhesive, paint, coating material, sealing material, casting material, coating material, and the like. In particular, by using the curable resin composition according to the present invention as a main component, it is possible to provide a composition having a low environmental load, high safety, and a high curing rate, so that the working time can be shortened. It can be suitably used for applications such as sealants or adhesive compositions as required. The “main body” means that a crosslinked network structure formed by condensation of a crosslinkable silyl group of the curable resin composition is a main component in the crosslinked network structure when the composition is cured.

  Moreover, when using as an adhesive precursor composition, tackifier resin can be further mix | blended with said curable resin composition, and it can mix uniformly, and can also obtain an adhesive precursor composition. In addition, when mixing curable resin composition and tackifying resin uniformly, for example, when compatibility of both is inadequate, you may use an organic solvent. As the organic solvent, alcohols such as ethanol, ethyl acetate, toluene, methylcyclohexane and the like are used. Further, when the compatibility between the curable resin composition and the tackifier resin is good or when the organic solvent is not preferred, the organic solvent may not be used. Moreover, an adhesive precursor composition can also be obtained without using tackifying resin for the use for which weak adhesiveness is calculated | required. A pressure-sensitive adhesive layer can be formed by applying the pressure-sensitive adhesive precursor composition thus obtained to the surface (one side or both sides) of a conventionally known tape base or sheet base and curing it. And an adhesive tape or an adhesive sheet is obtained.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to an Example.

-Preparation of curable resin (curable resin P1 according to the present invention)
As the curable resin P1, a resin (Exastar S2420 manufactured by Asahi Glass Co., Ltd.) having a main chain of polyoxypropylene and having a methyldimethoxysilyl group at the terminal was prepared.

(Curable resin P2 according to the present invention)
“GENIOSIL STP-E10” (manufactured by Wacker Chemie AG., Having a molecular weight of about 10,000 converted from an equivalent amount of methoxy group) having a main chain of polyoxypropylene and a terminal α-silyl structure of methyldimethoxysilyl group Got ready. The curable resin P2 is a curable resin having an α-silane structure in the molecule.

-Preparation of tin compound Neostan U-830 and Neostan S-1 made by Nitto Kasei Co., Ltd. were prepared as the octyltin compound (B) according to the present invention.
For comparison, SCAT-27 manufactured by Sansha Co., Ltd. was prepared as a butyltin compound.

-Preparation of aminosilane compound (C) As aminosilane, 3-aminopropyltrimethoxysilane was prepared.

(Example)
Each component was weighed at a blending ratio shown in Table 1 (numbers represent parts by mass), and these were rapidly mixed for 30 seconds to prepare a curable resin composition, and the skinning time was measured. For the skinning time, the curable resin composition is left in an atmosphere of 23 ± 1 ° C. and a relative humidity of 50 ± 5%, and the surface is lightly touched with a fingertip degreased with ethanol. However, it calculated | required as time until it stops adhering to a fingertip (based on JISA1439).

  From the results of Table 1, it can be seen that the curable resin composition according to the present invention exhibits practically sufficient curability while using an octyltin compound that is free from the risk of mixing with a tributyltin compound.

The curable resin composition according to the present invention can be used for all applications to which conventional curable resins have been applied. For example, it can be used as an adhesive, sealant, pressure-sensitive adhesive, paint, coating material, sealing material, casting material, coating material, and the like.

Claims (6)

A curable resin (P1) containing a crosslinkable silyl group-containing functional group represented by the following formula (1) in the molecule;
A curable resin (P2) containing a crosslinkable silyl group-containing functional group represented by the following formula (2) in the molecule;
An octyltin compound (B);
An aminosilane compound (C) having an amino group and a crosslinkable silyl group in the molecule as represented by the compound represented by the following formula (3);
A curable resin composition characterized by containing no tributyltin compound.

_{^{-X-SiR 1 (OR 2)}} 2 ··· formula (1)
(However, X is a hydrocarbon group having 2 or more carbon atoms, R ¹ is a hydrocarbon group having 1 to 10 carbon atoms, R ² is a phenyl group, an alkyl group having 1 to 6 carbon atoms, and 2- ( Butoxy) one or more groups selected from organic groups having 1 to 10 carbon atoms represented by ethyl group

^{_{-W-CH 2 -SiR 3 a (}} OR 4) 3-a ··· formula (2)
(W is a bonding functional group in which a hetero atom having a lone pair is bonded to a methylene group bonded to a silicon atom contained in a crosslinkable silyl group, and R ³ is a hydrocarbon having 1 to 10 carbon atoms. R ⁴ is a group of at least one selected from a phenyl group, an alkyl group having 1 to 6 carbon atoms, and an organic group having 1 to 10 carbon atoms typified by 2- (butoxy) ethyl group, 0, 1 or 2 are shown respectively)

R ⁵ R ⁶ N—R ⁷ —SiR ⁸ _b (OR ⁹ ) _3-b Formula (3)
(However, R ⁵ and R ⁶ are organic groups or hydrogen atoms, R ⁷ is an organic group in which a hetero atom is not bonded to a carbon atom bonded to a silicon atom contained in a crosslinkable silyl group, and R ⁸ is a carbon number. 1 to 10 hydrocarbon groups, R ⁹ is a kind selected from a phenyl group, an alkyl group having 1 to 6 carbon atoms, and an organic group having 1 to 10 carbon atoms typified by 2- (butoxy) ethyl group The above groups, b represents 0, 1 or 2, respectively)
  The curable resin composition according to claim 1, wherein the curable resin (P1) further contains a urethane bond and / or a urea bond in the molecule.   In the said Formula (2), it is a = 1, The curable resin composition of Claim 1 or 2 characterized by the above-mentioned.   A sealant composition comprising the curable resin composition according to any one of claims 1 to 3 as a main component of a curable component.   The adhesive composition which has the curable resin composition as described in any one of Claims 1-3 as a main component of a sclerosing | hardenable component. The adhesive precursor composition which uses the curable resin composition as described in any one of Claims 1-3 as a main component of a sclerosing | hardenable component.